Triazinyl azo dyestuffs



United States atent F 3,004,022 :I'RIAZINYL AZO DYESTUFFS William ElliotStephen, Manchester, England, assignor to Imperial Chemical IndustriesLimited, London, England, a corporation of Great Britain v Np Drawing.Filed Jan. 17, 1958, Ser. No, 709,453 Clauns priority, application GreatBritain Jan. 23, 1957 6 Claims. (Cl. 260153) This invention relates tonew azo dyestuffs and more particularly it relates to new monoazodyestufis which are valuable for the production of fast redcolour-ations on textile materials.

The present invention is a modification of the invention described inUnited Kingdom specification No. 785,222. In the said specificationthere are described certain monoazo dyestuffs containing a1-(2':4-dichloro-s-triazinylamino-)8-hydroxynaphthalene monoordi-sulphonic acid residue which are valuable dyestuffs for cel'lulosictextile materials, especially when applied in accordance with the dyeingand printing processes described in Belgian specifications Nos. 543,218,556,709 and 556,819. When so applied, the dyestuffs described in UnitedKingdom specification No. 785,222 are believed to become chemicallybound to the textile material, the resultant coloured textile materialsbeing very fast to severe Washing treatments. However, further study ofthese dyestuffs has revealed that, when the coloured dyeings and printsobtained therefrom by the processes indicated above are stored in aslightly moist, acidic atmosphere, as is sometimes found in textilewarehouses used for the storage of coloured textile materials, a smallproportion of colouring matter, probably a decomposition product of thedyestuff, becomes loosely attached to the textile material, and mayreadily be removed therefrom by mild washing treatments. Moreparticularly, in the case of the printed textile materials there is atendency of such loosely attached colouring matter to migrate so thatadjacent portions of the textile material become stained.

It is a purpose of the present invention to provide dyestuffs which,whilst having in the main the desirable properties of the dyestuffs ofUnited Kingdom specification No. 785,222, are superior to thosedyestuffs and dyestufrs of closely related structure thereto which areknown from the prior art, in respect of the fastness to moist, acidatmospheres of the dyeings and prints obtained from said dyestuffs bythe processes described in the Belgian specifications named above.

Thus according to the present invention there is provided themodification in or improvement of the invent-ion described in UnitedKingdom specification No. 785,222 whereby there are provided, as newdyestuffs, the monoazo compounds represented in the free acid form bythe formula:

Formula I wherein A stands for an aryl radical which may be substitutedother than with hydroxyl, amino or monoalkylamino groups, thenaphthalene nucleus contains one or two sulphonic acid groups, R standsfor a hydrogen atom or hydrocarbon radical, Q stands for a morp-phenylene radical which may be substituted for example by methyl and Xstands for a halogen atom.

Thus in the above formula, A may represent, for example, a benzene or analphaor beta-naphthalene nu- 3,004,022 Patented Oct. 1O, 1961 ICC cleuswhich may also be substituted, for example, by halogen such as chlorine,alkyl such as methyl,'trifiuor o-, methyl, alkoxy such as rnethoxy,*aryloxy such as phenoxy, and more especially Amay containelectronegative substituents, such as nitro groups, sulphamyl or monoor(ii-substituted sulphamyl groups, carboxylic acid, carboxylic ester,carbamyl or 1110110 or di-substituted carbamyl groups and above all bysulphonic acid groups. Dyestuffs which contain an electronegative group,and in particular a sulphonic acid group, ortho to the azo group, form apreferred class of the new dyestufis.

As hydrocarbon radicals represented by R there are preferred unbranched'alkyl radicals of 6 carbon atoms or less, for example methyl, ethyl,n-butyl and n-hexyl radicals.

X may represent, for example a chlorine or a bromine atom.

According to a further feature of the invention there is provided aprocess for the manufacture of new monoazo dyestuffs from, as startingmaterials, substantially equimolecular proportions of a cyanuric halide,a compound which in its free acid state is represented by the formula:

Formula II wherein the naphthalene nucleus contains one or two sulphonicacid groups, and Q and R have the meanings stated above, and adiazotised aromatic primary amine which may contain substituents otherthan hydroxyl or monoalkylamino groups, which comprises interacting thecompound represented by Formula II with either of the two startingmaterials and then interacting the product so obtained with the thirdstarting material.

Thus in the above process the compound represented by Formula II may befirst used as a coupling compo nent and interacted with the diazotisedamine bythe commonly-used methods for the manufacture of azo compoundsand then the azo compound so obtained interacted with the cy-anurichalide; or the compound represented by Formula II may be firstinteracted with a cyanuric halide and then the product so obtained isused as a coupling component and interacted with the diazotised amine,using the commonly-used methods for obtaining azo compounds.

As examples of cyanuric halides which may be used, there may bementioned cyanuric chloride and cyanuric bromide.

As examples of aromatic primary amines which may be diazotised for usein the above process there may be mentioned orthanilic acid, sulphanilicacid, aniline-2:5- disulphonic acid, 4-chloroaniline-Z-sulphonic acid,5-chlo-. ro-4-rnethylaniline-Z-sulphonic acid,4-methylaniline-2-sulphonic acid, 4-chloro-5-methylaniline-2-sulphonicacid, 3-amino-4-sulphobenzotrifluoride, 3 :4-dichloroaniline-6-sulphonic acid, 4-aminoanisole-3-sulphonic acid,3-aminoanisole-4-sulphonic acid, 3-methylaniline-4 sulphonic acid,1-naphthylamine-Z-sulphonic acid, 2-naphthylamine-3r6- disulphonic acidand Z-naphthylamine-l-sulphonic acid.

As examples of amino compounds of Formula II which may be used there maybe mentioned 1-(3-aminobenzoylamino) -8-hydroxynaphthalene-3 :6- and .46-disulphonic acids, l-(4-aminobenzoylamino)-8-hydroxynaphthalene-3:6-and 4:6-disulphonic acids, 1-(3'- aminoben zoylamino)-8-hydroxynaphthalene-2:4-disulpl1onic acid and l-(3'-aminobenzoylamino)-8-hydroxynaphthalene-6- sulphonic acid.

Although, in general it is preferred to use equimolecular proportions ofthe reactants, it is sometimes found preferable, in order to improve theyield or quality of the product, to use a slight excess, up to 10% byweight, of one reactant over the weight which is theoreticallyequivalent to the weight of the other reactant present.

In carrying out the above process, the product obtained by the firstinteraction may, if desired, be isolated but in general, it is preferredto interact it in situ with the third starting material.

When the compound represented by Formula II is first interacted with thediazotised amine, the interaction is preferably carried out in thepresence of an alkali, for example sodium carbonate. However, when thecou pling is carried out as the second interaction, using as couplingcomponent the interaction product of the cyanuric halide and thecompound represented by Formula II, it is preferred to use a reactionmedium as weakly alkaline as will allow the coupling to take placeefi'iciently, so that side-reactions, especially the loss of halogenfrom the triazine residue, are reduced to a minimum. In general areaction medium having a pH between 6 and 8 is preferred when thecoupling is carried out as the second interaction.

Whether the cyanuric halide is employed as a reactant in the first orthe second interaction of the process, the interaction is preferablycarried out in aqueous medium at a temperature between C. and 5 C. Ifdesired, an acid-binding agent for example sodium carbonate, may beadded to the medium.

It is generally preferable to isolate the new dyestuffs from the mediain which they have been formed at a pH from 6 to 8 and it has been foundthat the loss of chlorine from the triazine rings in the dyestuffs canbe reduced considerably by addition of certain bulfering agents whichgive a pH value between 6 and 8 and in particular by those which give apH of about 6.5. These buffering agents for example mixtures of disodiumhydrogen phosphate and sodium dihydrogen phosphate or of disodiumhydrogen phosphate and potassium dihydrogen phosphate may be added atany suitable time during the manufacture of the new dyestuffs, but aconvenient procedure comprises addition of sufficient of an acid-bindingagent such as sodium carbonate to the reaction mixture to give a pHbetween 6 and 8, then addition of buffering agent and then salt toprecipitate the dyestutf, isolation of the latter by filtration andaddition of more buffering agent to the dyestuif paste before drying.

The drying of the dyestutf paste is preferably carried out at atemperature below 65 C.

The new monoazo dyestuffs, in the form of the alkali metal salts aresoluble in water, and like the dyestuffs described in United Kingdomspecification No. 785,222 they may be used to colour silk, wool,regenerated protein and cellulosic textile materials for example cotton,linen and viscose rayon, by treating the textile material with anaqueous solution (which may be a thickened printing paste) of thedyestuif in conjunction with a treatment with an acid-binding agent, forexample sodium hydroxide, potassium phosphate, sodium carbonate orsodium bicarbonate. The treatment with the acid-binding agent may becarried out prior to, simultaneously with or after the treatment withthe dyestuff.

The new dyestuffs may also be applied to silk, wool, regeneratedprotein, polyamide and modified polyacrylonitrile textile materials, bythe conventional dyeing methods used for those textile materials, thatis by dyeing from weakly acid or neutral dyestuif solutions, for exampledyestuff solutions containing acetic acid, formic acid, sodium sulphateor ammonium acetate.

The dyestuffs may also be applied to silk, wool and regenerated proteintextile materials by the conventional printing methods used for thosematerials.

When so applied, they give fast level red shades, which havesubstantially the same degree of fastness to washing and to light, asthose from the dyestuffs of the said specification.

The invention is illustrated but not limited by the following examplesin which parts and percentages are by weight:

EXAMPLE 1 A solution of 18.6 parts of cyanuric chloride in parts ofacetone is added to a stirred mixture of 200 parts of water and 300parts of crushed ice and then 2 parts of 2 N hydrochloric acid areadded. To the suspension of cyanuric chloride so formed there is addedin 40 minutes a solution of 48.2 parts of the disodium salt of1-(3-amin0benzoylamino)-8-hydroxynaphthalene- 3:6-disulphonic acid in240 parts of Water made faintly alkaline to Brilliant Yellow paper bythe addition of sodium carbonate. The temperature of the mixture is keptbetween 0 C. and 5 C. throughout the process.

The mixture is stirred for 2 to 3 hours until no cyanuric chloride ispresent and then there is added a suspension of the diazo compound from16.45 parts of aniline-2- sulphonic acid.

The mixture is stirred at a temperature between 0 C. and 5 C. andsufficient sodium carbonate is added to change the pH of the mixture to5. Common salt is then added at the rate of 15 lb. for every 10 gallonsof mixture and then more sodium carbonate is gradually added over 2hours to raise the pH of the aqueous medium to about 7.5 and to maintainit in this region until the coupling reaction is completed. A solutioncontaining 7.0 parts of disodium hydrogen phosphate and 12.5 parts ofpotassium dihydrogen phosphate in 100 parts of water is then added. Themixture is then stirred for 30 minutes, filtered and the residue isdried at 30 C.

The dyestufi so obtained contains 1.88 organically bound chlorine atomsfor each azo group. It may be applied to cotton by padding the fabricwith an aqueous solution of the dyestulf, drying, subsequently passingthe dried fabric through a 1% solution of caustic soda saturated withsodium chloride and afterwards steaming it for 1 minute. There is thusobtained a bright bluish-red colouration possessing good fastness tosevere washing and to light.

EXAMPLE 2 If the process described in Example 1 is repeated, using 24.0parts of aniline-2:5-disulphonic acid in place of the 16.45 parts ofaniline-Z-sulphonic acid, and the amount of common salt added to thecoupling mixture is raised to 20 lb. for every 10 gallons of volume, adyestuff is obtained which contains 2.0 organically bound chlorine atomsfor each azo group present. It dyes cotton by the method described atthe end of Example 1 in slightly yellower shades but having similar goodfastness to severe washing and to light.

EXAMPLE 3 If in the process of Example 1 the 48.2 parts of the disodiumsalt of 1-(3'-aminobenzoylamino-) 8-hydroxynaphthalene-3:6-disulphonicacid are replaced by 48.2 parts of the disodium salt of1-(4'-aminobenzoylamino-)- 8-hydroxynaphthalene-3:6-disulphonic acid andafter adding the suspension of the diazo compound and adjusting the pHof the coupling mixture to 5, common salt is added at the rate of 20 lb.for every 10 gallons of mixture and the subsequent procedure is thatdescribed in Example 1, then a dyestutf is obtained which contains 1.90organically bound chlorine atoms for each azo group present. Thisdyestuif when applied to cotton by the method described in Example 1gives bright bluish red shades with good fastness to washing and tolight.

EXAMPLE 4 A solution of 19 parts of cyanuric chloride dissolved in 108parts of acetone is added to a stirred mixture of 300 parts of water and300 parts of crushed ice. To the suspension of cyanuric chloride soformed there is added in 40 minutes a solution of 48.2 parts of thedisodium salt of 1-(3'-aminobenzoylamino)-8-hydroxynaphthalene-3:6-disulphonic acid in 800 parts of water made faintly alkaline toBrilliant Yellow paper by addition of sodium 5 carbonate. Thetemperature of the mixture is kept between C. and C. throughout theprocess.

The mixture is stirred for 1 to 2 hours until no cyanuric chloride ispresent and then there is added a suspension of the diazo compound from21.05 parts of 5-chloro-4- methylaniline-Z-sulphonic acid.

The mixture is stirred at a temperature between 0" C. and 5 C. andsufficient sodium carbonate is added to change the pH of the mixture to7. More sodium carbonate is gradually added to raise the pH to 7 and tomaintain it in this region until the coupling reaction is completed. Asolution containing 7.0 parts of disodium hydrogen phosphate and 12.5parts of potassium dihydrogen phosphate in 100 parts of water is thenadded. The mixture is stirred for 30 minutes, filtered and the residueis dried at C.

The dyestufi? so obtained contains 1.96 organically bound chlorine atomsfor each azo group. It dyes cotton by the method described at the end ofExample 1 giving a bright bluish red colouration possessing goodfastness to 25 washing and to light.

In the following table there are described in column 2 the shadesobtained from further dyestufis of the invention, obtained by theprocedure described in Example 4 but substituting the molecularlyequivalent amount of the diazonium compound from the amine named incolumn 1.

All dyestuffs so obtained contain 2.0 organically bound chlorine atomsfor each azo group.

EXAMPLE 14 A solution of 18.6 parts of cyanuric chloride in 130 parts ofacetone is added to a stirred mixture of 170 parts of water and 170parts of crushed ice. To the suspension of cyanuric chloride so formedthere is added during 40 minutes a solution of 73.4 parts of thetrisodium salt of the arninoazo dyestuif obtained by coupling, in thepresence of sodium acetate, diazotised aniline-Z-sulphonic acid with1-(N-n-butyl-N- 3'-aminobenzoylamino) -8-hydroxynaphthalene 3:6disulphonic acid in 850 parts of water made faintly alkaline toBrilliant Yellow paper by the addition of sodium carbonate. Thetemperature of the mixture is kept between 0 C. and 5 C. throughout theprocess. I

The mixture is stirred for 1 hour, neutralised to pH 7 by the additionof sufiicient sodium carbonate and stirring is continued for a further 2hours until no cyanuric chloride is present, the pH being maintained at7 by further additions of sodium carbonate. A solution containing 7.0parts of disodium hydrogen phosphate and 12.5 parts of potassiumdihydrogen phosphate in 100 parts of water is then added. The dyestuficontain 2.0 organically bound 7 chlorine atoms for each azo link anddyes cotton by the method described at the end of Example 1 in reddishorange shades.

EXAMPLE 15 If the process described in Example 1 is repeated using 48.2parts of the disodium salt of1-(3-aminobenzoylamino)-8-hydroxynaphthalene-4:6-disulphonic acid inplace of the 1-(3'-aminobenzoylamino)-3:6-disulphonic acid, and theamount of common salt added to the coupling mixture is increased to 20lb. for every 10 gallons of volume, a dyestufi is obtained whichcontains 2.0 organically bound chlorine atoms for each azo grouppresent. It dyes cotton by the method described at the end of Example 1in yellower shades having good fastness to washing and light.

What 1 claim is: V v

1. Dyestufis represente in their tree acid form by the formula: 1

A stands for a radical selected from the group consisting ofunsubstituted naphthyl and sul-fonated naphthyl radicals, phenylradicals and phenyl radicals carrying up to three substituents selectedfrom the group consisting of chlorine, methyl, trifluoromethyl, methoxy,phenoxy, nitro, sulfamyl, carbarnyl, carboxy, and sulfonic acid groups;

n is a small whole number having a value from 1 to 7;

Q is a member selected from thegroup consisting of mand p-phenyleneradicals; and,

one of the radicals represented by Y and Y is selected from the groupconsisting of hydrogen and sulfonic acid, and the other is hydrogen.

2. The dyestuif having the formula:

3. The dyestuff having the formula:

HOaS SOaH ll CHaQN=N Cl HOaS SO:H

5. The dyestufi having the formula:

8 6. The dyestuff having the formula:

N N NH-(fi 3-01 NH-C cC1 5 N H l N N Ell 3:0 (:1 (i=0 (:1 503B r m ZITH10 N=N Hogs SO3H 15 Soil References Cited in the file of this patentUNITED STATES PATENTS 2,835,663 Benz May 20, 1953 2,892,829 Stephen June30, 1959 FOREIGN PATENTS 1,133,883 France Nov. 26, 1956

1. DYESTUFFS REPRESENTED IN THEIR FREE ACID FORM BY THE FORMULA: